FULL PAPER
ture as eluent to obtain first 7b and second 4b. After removal of
all volatile materials, compounds 7b (Rf = 0.67) and 4b (Rf = 0.52)
were isolated as orange solids.
Supporting Information (see footnote on the first page of this arti-
cle): Figures and CIF files giving additional experimental and crys-
tallographic data.
Compound 4b: Yield 0.254 g (0.40 mmol, 18% based on 2b), m.p.
1
183 °C. H NMR (CDCl3): δ = 2.43 (s, 3 H, CH3), 4.21 (pt, JH,H
Acknowledgments
= 1.8 Hz, 4 H, C5H4), 4.23 (s, 10 H, C5H5), 4.48 (pt, JH,H = 1.8 Hz,
4 H, C5H4), 7.27 (s, 2 H, 2/5-H), 7.32–7.34 (m, 2 H, C6H4/o-CH3),
7.78–7.80 (m, 2 H, C6H4/m-CH3) ppm. 13C{1H} NMR (CDCl3): δ
= 21.7 (CH3), 64.8 (Ci–C5H4), 69.0 (C5H4), 70.1 (C5H5), 71.5
(C5H4), 76.9 (CϵC), 91.4 (CϵC), 113.2 (C-3/4), 122.6 (C-2/5),
127.2 (C6H4/m-CH3), 130.2 (C6H4/m-CH3), 135.2 (C–S), 145.7 (C–
The authors are grateful to the Fonds der Chemischen Industrie
(FCI) for financial support. M. K. thanks the Fonds der
Chemischen Industrie for
a fellowship. Dipl.-Chem. Dieter
Schaarschmidt is thanked for many fruitful discussions.
CH ) ppm. IR (NaCl): ν = 3140 (w, νC–H), 3094 (w, νC–H), 2964
˜
3
as
[1] M. Iyoda, T. Kondo, T. Okabe, H. Matsuyama, S. Sasaki, Y. A.
Kuwatani, Chem. Lett. 1997, 26, 35–36.
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Chem. 2011, 50, 10623–10632.
as
(w,
ν
), 2923 (w), 2853 (w,
ν
), 2215 (m, νCϵC), 1595 (w),
), 1319 (m), 1286 (w), 1213 (w),
CH3
CH3
as
1448 (w), 1411 (w), 1378 (m,
ν
SO2
s
1190 (m), 1173 (s, νSO2), 1121 (w), 1105 (w), 1091 (m), 1065 (s),
1027 (m), 1002 (m), 966 (w), 926 (w), 814 (s, γC–H), 761 (w), 702
(m), 671 (m), 585 (s), 534 (m) cm–1. UV/Vis (CHCl3): λ = 231, 279,
445 nm. HRMS (ESI-TOF): calcd. for C35H27Fe2NO2S 637.0457;
found 637.0477 [M]+.
[3] a) D. Miesel, A. Hildebrandt, M. Korb, P. J. Low, H. Lang,
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3037–3046; c) A. Hildebrandt, S. W. Lehrich, D. Schaar-
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11444–11448; Angew. Chem. Int. Ed. 2011, 50, 11248–11252.
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T. Rüffer, A. Spannenberg, H. Lang, U. Rosenthal, Chem. Eur.
J. 2012, 18, 12672–12680.
Crystal Data for 4b: Suitable single crystals of 4b were obtained by
the diffusion of methanol into a solution of 4b in dichloromethane
at ambient temperature. C35H27Fe2NO2S, Mr = 637.34 gmol–1,
¯
0.40ϫ0.35ϫ0.35 mm, triclinic, P1,
λ
=
0.71073 Å,
a =
9.3833(5) Å, b = 10.7499(8) Å, c = 14.1386(7) Å, α = 78.728(5)°, β
= 84.988(4)°, γ = 79.113(5)°, V = 1371.56(14) Å3, Z = 2, ρcalcd.
=
1.543 gcm–3, μ = 1.169 mm–1, T = 100(2) K, Θ range = 2.94–
25.50°, reflections collected 8951, independent 5061 (Rint = 0.0200),
R1 = 0.0291, wR2 = 0.0707 [IՆ2σ(I)].
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5653.
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670; I. M. Bruce, Coord. Chem. Rev. 1997, 166, 91–119; c) M.
Ratner, J. Jortner, Molecular Electronics, Blackwell Science,
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791–804; e) P. C. Collier, W. E. Wong, M. Belohradsky, M. F.
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2002, 41, 4378–4400; g) N. Robertson, C. A. McGowan, Chem.
Soc. Rev. 2003, 32, 96–103.
Compound 7b: Yield 0.300 g (0.59 mmol, 26% on the basis of 2b),
1
m.p. 160 °C. H NMR (CDCl3): δ = 2.43 (s, 3 H, CH3), 4.23 (pt,
JH,H = 1.8 Hz, 2 H, C5H4), 4.24 (s, 5 H, C5H5), 4.48 (pt, JH,H
=
1.8 Hz, 2 H, C5H4), 7.16 (d, JH,H = 2.5 Hz, 1 H, 5-H), 7.28 (d, JH,H
= 2.5 Hz, 1 H, 2-H), 7.32–7.34 (m, 2 H, C6H4), 7.76–7.78 (m, 2 H,
C6H4) ppm. 13C{1H} NMR (CDCl3): δ = 21.7 (CH3), 64.4 (Ci–
C5H4), 68.9 (C5H4), 70.1 (C5H5), 71.6 (C5H4), 75.8 (CϵC), 92.3
(CϵC), 105.3 (C-3), 112.9 (C-4), 119.7 (C-5), 122.8 (C-2), 127.2
(C6H4), 130.3 (C6H4), 135.1 (C–S), 145.8 (C–CH3) ppm. IR (NaCl):
[8] A. Hildebrandt, T. Rüffer, E. Erasmus, J. C. Swarts, H. Lang,
Organometallics 2010, 29, 4900–4905.
as
ν = 3138 (m, νC–H), 3095 (w, νC–H), 2955 (w,
ν
CH3
), 2923 (w),
˜
2854 (w, sνCH3), 2223 (m, νCϵC), 1595 (m), 1555 (w), 1494 (w), 1448
[9] A. Hildebrandt, D. Schaarschmidt, H. Lang, Organometallics
2011, 30, 556–563.
as
s
(w), 1379 (s), 1309 (s,
ν
SO2
), 1217 (s), 1189 (s), 1174 (s, νSO2),
[10] A. Hildebrandt, H. Lang, Dalton Trans. 2011, 40, 11831–
1090 (w), 1074 (s), 1047 (m), 1020 (m), 1002 (w), 960 (m), 916 (w),
813 [m (γ = C–H)], 793 (m), 718 (w), 701 (w), 671 (s), 596 (s), 585
(m), 536 (m) cm–1. UV/Vis (CH2Cl2): λ = 230, 265, 445 nm. HRMS
(ESI-TOF): calcd. for C23H18BrFeNO2S 506.9587; found 506.9610
[M]+.
11837.
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L. van As, J. C. Swarts, H. Lang, Organometallics 2012, 31,
6373–6380.
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J. Org. Chem. 1990, 55, 6317–6328; b) C. Zonta, F. Fabris, O.
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Crystal Data for 7b: Suitable single crystals of 7b were obtained by
the diffusion of methanol into a solution of 7b in dichloromethane
at ambient temperature. C23H18BrFeNO2S, Mr = 508.20 gmol–1,
¯
0.50ϫ0.40ϫ0.35 mm, triclinic, P1,
λ
=
=
0.71073 Å,
a
=
=
9.6481(12) Å,
b
=
11.0576(12) Å,
c
11.3090(14) Å, α
76.213(10)°, β = 65.546(13)°, γ = 69.762(11)°, V = 1024.1(2) Å3, Z
= 2, ρcalcd. = 1.648 gcm–3, μ = 2.809 mm–1, T = 100(2) K, Θ range
= 3.52–25.49°, reflections collected 6964, independent 3799 (Rint
0.0244), R1 = 0.0277, wR2 = 0.0678 [IՆ2σ(I)].
=
[16] a) T. Fukuda, E. Sudo, K. Shimokawa, M. Iwao, Tetrahedron
2008, 64, 328–338; b) V. Stockmann, K. L. Eriksen, A.
Fiksdahl, Tetrahedron 2008, 64, 11180–11184; c) A. Fürstner,
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CCDC-967395 (for 2c), -967396 (for 5), -967397 (for 1b), -967398
(for 2b), -967399 (for 3b), -967400 (for 7b), -967401 (for 4b), and
-967402 (for 3a) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Eur. J. Inorg. Chem. 2014, 1051–1061
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